WO2012136508A1

WO2012136508A1 - Graphitised carbon moulded body having low thermal conductivity, method and slip for the production thereof

Info

Publication number: WO2012136508A1
Application number: PCT/EP2012/055371
Authority: WO
Inventors: Heribert Walter; Verena MERKLINGER; Dominik RIVOLA; Stefan Fries; Oswin ÖTTINGER
Original assignee: Sgl Carbon Se
Priority date: 2011-04-08
Filing date: 2012-03-27
Publication date: 2012-10-11
Also published as: DE102011007075A1

Abstract

The invention relates to an aqueous-based slip comprising dispersed particles containing at least one sinter-active carbon. According to the invention, the sinter-active carbon contains a pitch having a total QI of less than 60%.

Description

Graphitierter carbon moldings of low thermal conductivity, a method and a slurry for its production

The invention relates to a graphitized carbon form body low thermal conductivity, a process for its preparation and a slurry for its preparation.

In a number of applications, materials are required which are chemically very stable and, moreover, have a low thermal conductivity. This is especially the case where temperature fluctuations strongly influence a process, such as single crystal growth. There support structures for Czochralski crystal growing systems are required, the geometric dimensions remain essentially constant during the process. Likewise, for example, charging equipment in furnace construction requires a material that not only resists the high temperatures in the furnace but also dissipates as little heat as possible from the furnace.

Conventionally, graphite-containing materials, such as in particular graphitized carbon materials, are used for such tasks. These are chemically largely inert even at high temperatures and have a relatively low thermal conductivity. However, graphite materials conventionally produced are not suitable for optimum thermal insulation and heat dissipation since present thermal conductivities of 50-150 W / mK are still too high.

In DE 1 904 381 an aqueous sludge or slurry is described in which so-called modified pitch is dispersed there. Modified pitch is produced by subjecting coal tar pitches, petroleum asphalts and other pitch-like matter produced as industrial by-products to heat treatment, solvent extraction and treatment with various materials such as ozone, oxygen, the air oxides of nitrogen, halogens, sulfur and sulfur compounds , DE 1904 381 also states that with this complicated shape be produced with it body. However, DE 1904381 at no point addresses the thermal conductivity of the shaped bodies produced and also does not describe the need to set a targeted thermal conductivity. With the in the DE

1904381 slip can be obtained no shaped body having a low thermal conductivity, which makes the moldings suitable to use them in the above fields of application.

The object of the invention is to provide a slurry with which graphitized carbon moldings can be produced, which have a low thermal conductivity, as well as such a shaped body and a method for its production.

The problem is solved with a slip according to claim 1. According to the invention, an aqueous-based slurry with dispersed particles containing at least one sintering-active carbon is proposed. The sintering carbon contains a pitch with a total Ql of less than 60%. With a slip according to the invention, surprisingly graphitized carbon moldings having a particularly low thermal conductivity can be produced. The total Ql represents the sum of primary, secondary and tertiary Ql. Ql (from English "c noline-insoluble") represents the portion of a pitch that is not soluble in quinoline.

Primary Ql is produced during the distillation process for coke production as a "carry over." Secondary Ql (also called thermal Ql) is formed in the further pitch distillation processes essentially at temperatures of about 300 to 400 ° C. and describes polycyclic condensed aromatics having a planar or spatial structure. Tertiary Ql is formed by a cross-linking process to stabilize the pitch raw material against swelling during carbonation, and the cross-linking of aromatic and aliphatic structures during stabilization increases quinoline insolubility.

Tertiary Ql tends to inhibit formation of higher graphitizability by freezing a low-order state. Thus, with the slip according to the invention, carbon moldings of low thermal conductivity can be obtained. shear conductivity, because the lower the degree of graphitization, the lower the thermal conductivity.

According to a very particularly preferred embodiment of the present invention, the slurry contains mesophase pitch and / or highly distilled pitch. Mesophase pitch is aromatic-rich pitch in the liquid crystalline phase. On the other hand, highly distilled pitch is a pitch having a volatile content devolatilized by a heat treatment. Preferably, the highly distilled pitch is oxidatively stabilized, which can be achieved, for example, by reacting the highly distilled pitch in the presence of a crosslinking agent, such as in air or in the presence of hydrogen peroxide, a halogen compound or a sulfur compound at a temperature greater than 100 ° C and in particular at a temperature of greater than 150 ° C for several hours or days of heat treatment is subjected. As a result, the aliphatic groups of the pitch are cross-linked by means of a stabilization process, which reduces the formation of pyrolysis gases in thermal processes and thus preserves larger proportions of the aliphatic structures. Such pitches show a reduced pyrolysis gas release in thermal processes and have softening points above 250 ° C. Mesophase pitch and highly distilled pitch have the advantageous ability, due to their low expandability, for use in a slip casting process, to give a shaped body with sufficiently high strength by carbonizing or graphitizing a green body without additional compaction by pressing or the like. The preservation of larger proportions of aliphatic structures hinders remodeling into aromatic structures and thus ultimately prevents the formation of a well-ordered remote structure. It forms a glassy or X-ray amorphous state. A highly distilled pitch is generally a pitch with only moderate heat treatment but depleted volatiles, which show reduced pyrolysis gas release by final cross-linking of the aliphatic groups by means of a stabilization process in thermal processes. Typically show these pitches softening points above 250 ° C. A high primary QI content is also advantageous because it inhibits the coagulation of pitched mesase and thus prevents the formation of a homogeneous long-range order in the graphitized state. This contributes to a low thermal conductivity of a carbon body from a slip according to the invention.

It may also be advantageous that the thermal Ql of the pitch including the primary Ql is 3 to 8% and the tertiary Ql including the thermal Ql - and thus also including the primary Ql - is at most 60%.

In principle, all the sintering carbons known to the person skilled in the art can be used in the slip according to the invention, with pitch, for example coal tar pitch or petroleum pitch and / or synthetically produced mesophase pitch, having proven particularly suitable for this purpose. Petroleum-derived pitches may advantageously have a particularly low total Q1 of, for example, less than 5%.

It may also be advantageous, according to a variant of the invention, to add the total Q1 by adding resins, e.g. Phenol resins and / or furan resins. Thus, the overall Ql can be lowered by a simple technical measure and thus also the graphitization. The resin addition can be done for example by admixing in the solid state. Instead of or in addition to resins, pitches having melting ranges below 180 ° C. or, for example, anthracene oils are also suitable.

Advantageously, the particles have a d ₅ o value of less than 4 pm, in particular less than 3 pm, very particularly of 2. This particle size range has proved to be particularly advantageous in order to obtain both a stable slip and, after the slip has been processed into a graphitized carbon molded article, particularly good material properties, such as pore sizes of less than 1 μm and high strength of, for example, up to 200 MPa , Preferably, the slip contains a dispersant from the group of electrostatically, sterically or electrosterically acting dispersants. These

Especially with the preferred small particle sizes, dispersants contribute to the formation of a stable suspension, that is to say stable slip, which is easy to process and has a decisive influence, especially with regard to the processing time. The dispensing agent has the task to improve the stirrability of the powder in a liquid, as well as to avoid the formation of agglomerates during stirring. Among other things, the chosen dispersant determines the long-term stability against agglomeration.

According to a further particularly preferred embodiment of the present invention, the sintering-active carbon contained in the slurry has a d ₅₀ particle diameter determined by static light scattering according to ISO 13320-1 of less than 3 μm, in particular between 1 and 2.5 μm, very particularly between 2 and 5 μm - look at 1 and 2.0 pm. Sintering carbon having such d ₅₀ particle diameter has been found to be particularly advantageous on the one hand to obtain a stable slurry, and on the other hand to slip-cast the slurry into a high-density, high-strength carbon molded article to give a low porosity and a small pore diameter. Due to this particle size, the microstructure in the green kidney from the slurry, for example, when pouring into a conventional gypsum mold, as it is known from the ceramic Schlickergießen her, already strong. In this case, particles of sinter-active carbon are strongly compressed by the suction effect of the plaster mold and smaller particles of sinter-active carbon are deposited in gussets between larger particles of sinter-active carbon. Sintering carbon having such d ₅₀ particle diameter can be easily prepared by wet milling.

Advantageously, the slip according to the invention contains from 50 to 70% by weight of sinter-active carbon, in particular from 55 to 65% by weight.

In a further development of the inventive concept, it is proposed that the slip according to the invention contains from 0.5 to 4% by weight and preferably from 1.5 to 2.5% by weight of dispersant. contains food. By such an amount of the dispersant, a sufficiently high dispersing agent concentration in the slurry is controlled to reliably prevent agglomeration of the carbon particles contained in the slurry according to the present invention, even if the carbon particles have a very small particle diameter of, for example, 2 to 4 pm.

In principle, all the electrostatically and / or electrosterically stabilizing dispersants known to the person skilled in the art can be used in the slip according to the invention. However, good results are obtained, in particular, when the slip contains as the electrostatic stabilizing dispersant a compound selected from the group consisting of sulfonates,

Phosphonates, anionic surfactants, cationic surfactants and mixtures of two or more of the aforementioned compounds. In particular, these dispersants have a large interaction length or range of interaction between the dispersed particles. In addition, the above dispersants enable a very good dispersion of carbon particles, even if the carbon particles have a very small particle diameter of, for example, 2 to 4 m.

Nonlimiting examples of anionic surfactants suitable as dispersants in the slip according to the invention are alkyl sulfates, alkyl sulfonates, alkyl carboxylates, aryl sulfates, aryl sulfonates, aryl carboxylates, alkylaryl carboxylates, alkylarylsulfates, alkylaryl sulfonates, alkyl ether sulfates, alkyl ether sulfonates, alkyl glyceryl ethers, alkylbenzenesulfonates, alkylsulfosuccinates, dialkylsulfosuccinates and mixtures of two or more of the aforementioned compounds. Preferably, the above compounds are alkali metal salts or alkaline earth metal salts. The alkyl constituents of these compounds are preferably C 6 -C 25 -alkyl groups and more preferably C 6 -C 6 -alkyl groups and the aryl constituents of these compounds are benzene or phenol groups. Examples of suitable sulfonates are those having the general formula R-SO 3 -X, wherein R is an aliphatic, alicyclic or arylaliphatic group having 1 to 50 carbon atoms and preferably having 1 to 25 carbon atoms or a heterocyclic group or aryl group with 6 to 25 carbon atoms and X is a metal, preferably an alkali or alkaline earth metal. Specific examples of suitable anionic surfactants are sodium lauryl sulfate and sodium dodecylbenzenesulfonate. Non-limiting examples of cationic surfactants suitable as dispersants in the slurry of the invention are quaternary ammonium compounds. These are in particular compounds of the general formula

(NR ¹ R ² R ³ R) ⁺ X ^- wherein each of R ¹ , R ² , R ³ and R ⁴ , the same or different, has an aliphatic, alicyclic, arylaliphatic, heteroaromatic or aryl group of 1 to 50 carbon atoms and preferably 1 to 25 carbon atoms and X is a metal, preferably an alkali or alkaline earth metal. Particularly preferred examples of such quaternary ammonium compounds are alkyltrimethylammonium salts, dialkyldimethylammonium salts, benzalkonium salts, esterquats and ethoxylated quaternary ammonium compounds, each of which can be used individually or in mixtures of two or more of the abovementioned compounds. Specific examples of suitable cationic surfactants are

Cetyltrimethylammonium bromide and benzalkonium chloride.

The abovementioned phosphonates may be, for example, compounds having one of the general formulas M ¹ H ₂ PO 3 and M ¹ M ² HPO 3, in which M ¹ and M ^{2 are} identical or different and independently of one another a metal, preferably an alkali - or alkaline earth metal, are.

In a further development of the inventive concept, it is proposed that the slip according to the invention contains from 0.5 to 4% by weight and preferably from 0.5 to 2% by weight of binder.

Non-limiting examples of suitable binders are compounds selected from the group consisting of polyethers, polyvinyl alcohols, polyolefins, monosaccharides, oligosaccharides, polysaccharides, preferably cellulose, and mixtures of two or more of the foregoing. Good results are obtained, in particular, when the binder has a weight-average molecular weight of at least 2,000, preferably of at least 3,000 and more preferably of at least 4,000. In addition, it has proved to be advantageous if the slip according to the invention has a solids content of from 20 to 80%, preferably from 40 to 80% and particularly preferably from 50 to 70%. In this case, preferably the main component, ie at least half of the solid of sinter-active carbon, preferably over 75%, for example, the entire solid.

The object is further achieved by a method according to claim 9. According to the method of the invention, an aqueous-based slurry having dispersed particles containing at least one sintering-active carbon material is prepared by milling a pitch having a total Ql of less than 60% to a particle size d _{50 of} less than 3 μm.

Preferably, the grinding is carried out as wet grinding. As a result, the particle sizes can be achieved particularly well. In addition, the sludge obtained can be further processed directly into an aqueous slip according to the invention.

Another object of the present invention is a method for

Making a carbon body by slip casting, which the

subsequent steps, preferably in the order presented, comprising: a) introducing the slip according to the invention into a porous casting mold, such as a plaster mold,

b) fragmentation,

d) removing the resulting green compact from the mold,

e) drying the green body and

f) carbonizing the green body.

The carbonization of the green compact in process step e) can be carried out in any manner known to the person skilled in the art. Preferably, the green compact is in the process step e) at a temperature of 600 to 1, 500 ° C and more preferably from 800 to 1 .100 ° C carbonized.

According to a further particularly preferred embodiment of the present invention, the carbonized in the process step e) molded article after the carbonization of the green compact according to process step e) at a temperature of 1 .500 to 3,100 ° C and preferably from 1 .800 to 2,400 ° C graphitized , Due to the relatively low graphitization temperatures a low thermal conductivity is achieved, although there is still a graphitization.

Furthermore, the present invention relates to a carbon body which is obtainable with the above-described slip according to the invention and in particular by the method according to the invention described above. A shaped carbon article according to the invention, which is preferably produced from a slip according to the invention, in particular with a

The method according to the invention is characterized in that it has a

Thermal conductivity at room temperature of at most 35 W / mK, in particular of at most 30 W / mK, more preferably from 8 to 25 W / mK has. Such a carbon molding can be used particularly well where high

Temperatures and / or chemically aggressive media are present and where at the same time a low dissipation of heat is desired. This is the case, for example, for supporting structures for Czochralski crystal growing systems, but also in the case of

Charge racks in the furnace construction.

According to a further particularly preferred embodiment of the present invention, the carbon body according to the invention has a density of 1.4 to 1.9 g / cm ³ , preferably from 1.6 to 1.8 g / cm ³ and more preferably from 1.65 to 1.75 g / cm ³ . This for a carbon body, in particular a graphitized carbon body, relatively low density is particularly advantageous for low thermal conductivity. Preferably, the carbon body has a (determined by the method of Maire and Mering) Graphitierungsgrad from -0.8 to 0.2, more preferably from 0 to 0, 1, most preferably from 0 to 0.01 at graphitization temperatures of 2800 ° C. In these Graphitierungsgraden both an advantageously low thermal conductivity is achieved, as well as the other desirable property of graphite, namely a high purity, because at the high graphitization temperatures impurities are removed from the carbon body. High purity is a prerequisite for many of the desired applications, such as Si crystal growth. Even at lower graphitization temperatures, such as about 2500 ° C, high purity is achieved using graphitization aids such as chlorides or halides which decompose carbides.

In a further development of the inventive concept, it is proposed that the carbon body according to the invention has a mean pore diameter of 0.05 to 2 μm, in particular 0.05 to 1.5 μm, preferably 0.08 to 1 μm, measured according to DIN 66133. Such a pore diameter of the carbon body according to the invention can be achieved in particular if the carbon contained in the slurry has a d ₅₀ particle diameter of 1 to 10 μm, preferably of 1.5 to 5 μm and particularly preferably of 2 to 3 μm, and the slurry in the slip casting process undergoes a total shrinkage of 10 to 25%, preferably from 15 to 25% and particularly preferably from 18 to 23%. The total shrinkage is composed of the shrinkage during drying, carbonation and graphitization and is at 20% total shrinkage, for example, about 3% for drying, about 14% for carbonization and about 6% for graphitization. These pore sizes, in particular in the preferred ranges, cause the carbon body to have a particularly low thermal conductivity and in the process the mechanical strength is not or hardly reduced.

The high strength of, for example, 70 to 150 MPa (determined in four-point bending) results from the very good sintering behavior of the slurry used according to the invention. The individual homogeneously constructed pitch grains have a low tendency to blaze and move towards each other during a sintering step, so that in addition to the compression during the suction through a plaster mold a further compaction takes place in the thermal process. In comparison systems with at least two carbon component, z. As pitch as a binder and a filler such as graphite or coke, the entire system can not perform a shrinkage that is greater than 8%. By contrast, in the case of the present invention, a shrinkage of more than 10, preferably more than 15, particularly preferably more than 20%, or even for example 50%, can be achieved.

The carbon body according to the invention preferably has a porosity of more than 10%, and preferably of more than 15%, measured by mercury porosimetry according to DIN 66133, such as 15 to 20%. Such a high overall porosity additionally increases the effect of the low thermal conductivity, while the mechanical strength remains high.

Such a high porosity of the carbon body according to the invention can be achieved in particular if the carbon contained in the slurry has a d ₅ o particle diameter of from 1 to 10 μm, preferably from 1.5 to 5 μm and particularly preferably from 2 to 3 μm , and the slip in the slip casting process undergoes a total shrinkage of 10 to 25%, preferably 15 to 25% and most preferably 18 to 23%.

For a better understanding of the invention, a concrete embodiment of the invention is shown below. This is not limiting, but is intended to explain the invention in more detail. A highly distilled pitch or Mesophasenpech that has been oxidatively stabilized in a fluidized bed reactor or a conventional heating furnace has a thermal Ql of 15% and a tertiary Ql of 45%. The pulverulent pitch is ground wet with a ball mill until an average particle size d ₅₀ of 2.5 μm is reached.

The slurry contained in water during the milling is adjusted with water so as to have a content of pitch of 60% by weight in the aqueous slurry. The dispersant used is an electrostatic disperser, in this example from the group of lignosulfonates. The amount of dispersant carries in this example 2.2 wt .-%. The binder used is PVA in the amount of 1% by weight.

The slurry is poured into a plaster mold, as is conventionally used in slip casting for ceramic slurry. In this example, a mold is used for a crucible with a diameter of 100 mm and a height of 170 mm. After 45 minutes, the slurry is poured out and left the resulting greenhorns left for a further 100 min. The green compact is then removed and dried to ambient humidity within one week. The dried body is carbo- nized at maximum temperatures of 800 ° C - 1 100 ° C and then graphitized at 2800 ° C. The degree of graphitization is determined radiographically iffractometrically by the method of Maire and Mering. In order to be able to determine the degree of graphitization, powder diffractometry is used. The samples are present in fine powders and are treated with Cu-Kc radiation. Through the reflected part of the radiation, a statement about the orientation of the crystals in a powder can be made (at which angle was the reflection and with which intensity). In carbon materials, the (002) peak is considered - the closer the material comes to the ideal graphite, the greater the intensity of the (002) peak. For this reason, a statement about the degree of graphitization with the help of this Peaklage is possible.

The degree of graphitization is calculated as follows: the angle at which 50% of the peak area is reached is selected and with the Bragg-Brentano equation error! Reference source not found. the lattice plane distance is calculated. n ^■ λ = 2 ^■ π ^■ d · sin 5 n diffraction order

λ: wavelength

d lattice spacing

diffraction angle This value is compared with the normalized values (see table), thereby determining the degree of graphitization.

Table: Normalization values for determining the degree of graphitization

The degree of graphitization is determined to be 0, 1 in this embodiment. The thermal conductivity of the graphitized molding is determined at room temperature to 25 W / mK. The density is about 1.75 g / cm ³

In a variant of the exemplary embodiment, an oxidatively stabilized pitch having a tertiary Q1 of about 1% is used, which, as described in the first exemplary embodiment, is processed into a slip, slip-poured, carbonized and graphitized. The result is a graphitization degree of -0.78, a thermal conductivity of 8 W / mK and a density of approximately 1.4 g / cm ³ .

In another alternative, mesophase pitch is added to the highly distilled pitch or completely replaced with mesophase pitch. In the latter case, to obtain a low total Ql ß-resin must be added. It is thus possible to achieve shaped bodies with similar properties as according to the first two variants of the exemplary embodiment.

Claims

claims

1 . An aqueous based slurry having dispersed particles containing at least one sinter active carbon, characterized in that the sinter active carbon contains a pitch having a total Ql of less than 60%.

2. slip according to claim 1, characterized in that the pitch

contains highly distilled pitch and / or mesophase pitch.

3. Slip according to claim 1 or 2, characterized in that the pitch is oxidatively stabilized.

4. Slip according to at least one of claims 1 to 3, characterized in that the thermal Ql of the pitch including the primary Ql is at most 20% and the tertiary Ql including the thermal Ql at most 50%, in particular 0.5 to 50%, completely in particular 1 to 45%.

5. A slurry according to at least one of claims 1 to 4, characterized in that the pitch contains a petroleum-derived pitch, such as petroleum pitch, or a coal tar pitch.

6. Slip according to at least one of claims 1 to 5, characterized in that the total Ql is lowered by adding a resin, in particular a thermosetting resin, such as phenolic resin or furan resin.

7. slip according to at least one of the preceding claims,

By doing so, that is

the sintering-active carbon has a d ₅₀ particle diameter determined by static light scattering according to ISO 13320-1 of 1 to 10 μm, in particular of 1 to 5 μm and very particularly of 2 to 3 μm.

8. slip according to at least one of the preceding claims,

By doing so, that is

this 50 to 70 wt .-%, in particular 55 to 65 wt .-%, sintering active

Contains carbon.

9. slip according to at least one of the preceding claims,

By doing so, that is

this 0.5 to 4 wt .-%, in particular 1, 5 to 2.5 wt .-% dispersant.

A slip according to at least one of the preceding claims, characterized in that the slip contains a dispersant from the group of electrostatically stabilizing and sterically stabilizing dispersants or a combination thereof.

1 1. A process for the preparation of an aqueous-based slip with dispersed particles containing at least one sintered carbon material, according to one or more of claims 1 to 8, characterized in that a pitch with a total Ql of less than 60% on a

Particle size d ₅₀ less than 4 m is ground.

A method according to claim 9, characterized in that the grinding is carried out as wet grinding.

A method for producing a carbon body by slip casting, comprising the following steps:

a) incorporation of a slip according to at least one of claims 1 to 8, in particular produced by a process according to claim 9 or 10 in a porous casting mold, such as a plaster mold, b) fragmentation,

c) removing the resulting green compact from the mold,

d) drying the green body and

e) carbonizing the green body.

14. The method according to claim 11,

characterized by the fact that

the green compact in step e) is carbonated at a temperature of 600 to 1500 ° C, in particular from 800 to 1100 ° C.

Method according to claim 11 or 12,

characterized by the fact that

the shaped body carbonized in step e) is subsequently added to a

Temperature of 1,500 to 2,800 ° C, in particular from 1,800 to 2,400 ° C graphitized.

Carbon body produced from an aqueous slurry, in particular according to at least one of claims 1 to 8, which is produced in particular by a process according to claim 9 or 10, wherein the carbon body is produced in particular by a process according to at least one of claims 11 to 13.

Carbon molded article according to claim 14, characterized in that it has a thermal conductivity at room temperature of at most 35 W / mK, in particular of at most 30 W / mK, very particularly from 8 to 25 W / mK.

Carbon shaped article according to claim 15, characterized in that it has a density of 1.4 to 1.9 g / cm ³ , in particular from 1.6 to 1.85 g / cm ³ , very particularly from 1.72 to 1.78 g / cm ³ .

19. Carbon body according to at least one of claims 14 to 16, characterized in that its degree of graphitization according to Maire and Mering of - 0.8 to 0.2, in particular from 0 to 0.1.